CN112691706A - Regeneration method of catalyst for preparing acetonitrile from ethanol - Google Patents
Regeneration method of catalyst for preparing acetonitrile from ethanol Download PDFInfo
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- CN112691706A CN112691706A CN202011555739.0A CN202011555739A CN112691706A CN 112691706 A CN112691706 A CN 112691706A CN 202011555739 A CN202011555739 A CN 202011555739A CN 112691706 A CN112691706 A CN 112691706A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000011069 regeneration method Methods 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 58
- 238000010926 purge Methods 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims 3
- 238000001354 calcination Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/20—Plural distinct oxidation stages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a regeneration method of a catalyst for preparing acetonitrile from ethanol. The catalyst regenerated by the method has the characteristics of less chemical property attenuation, online operation and the like. The invention adopts the following steps: a regeneration system using an inert gas to fill the catalyst; roasting a catalyst to be regenerated at a certain temperature, and simultaneously purging the system in 5 stages by using one or more gases containing organic amine, oxygen, water vapor and ethanol at a certain flow rate as an activating gas (the 1 st to 3 rd stages are mixed gas of oxygen and organic amine with different volume concentration ratios, the 4 th stage is water vapor, and the 5 th stage is mixed gas of water vapor and ethanol); and when the gas outlet composition of the activated gas is consistent with the gas inlet after each stage is finished, continuously purging for a certain time, and finishing regeneration. The catalyst has good regeneration effect, simple operation and wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst regeneration, and particularly relates to regeneration of a catalyst for preparing acetonitrile from ethanol.
Background
Acetonitrile is an organic nitrile, and the most obvious function is to serve as a solvent, including a solvent for synthetic fibers, a solvent for some special coatings, a solvent for removing substances such as tar, phenol and the like, a solvent for extracting butadiene, a solvent for extracting fatty acid from animal and vegetable oil, a solvent for preparing vitamin B1, an active medium solvent of amino acid, a solvent capable of replacing a chlorinated solvent and a solvent for synthesizing acrylonitrile fibers. Extracting agent for C4 fraction, extracting agent for butadiene and fatty acid, and alcohol denaturant in synthetic rubber industry. Also in textile dyeing, vinyl paints, brightening engineering, perfume manufacture and the manufacture of photosensitive materials.
The patent with application number 200910031481.1 introduces a method for synthesizing acetonitrile by ethanol ammoniation, raw materials ethanol and ammonia are vaporized and preheated to 100 ℃ and 200 ℃, two raw materials are mixed and reacted to obtain acetonitrile, the reaction adopts an ethanol ammoniation catalyst with silicon dioxide as a carrier, and the reaction molar ratio of the two raw materials is ethanol: ammonia 1: 0.8-1.2.
At present, a regeneration method of the catalyst for preparing acetonitrile by ethanol does not exist, and the invention fills the blank. The method disclosed by the invention is simple to operate, high in activity after the catalyst is regenerated, and suitable for online regeneration operation.
Disclosure of Invention
The invention discloses a regeneration method of a catalyst for preparing acetonitrile from ethanol. The method is simple to operate, the activity of the regenerated catalyst is high, and the method is suitable for online regeneration operation.
The invention provides a regeneration method of a catalyst for preparing acetonitrile by ethanol, which is characterized in that a regeneration system of the catalyst is filled with inert gas, and gas feed liquid and the like related to the reaction of the previous system are discharged; roasting the catalyst to be regenerated at a certain temperature, wherein the roasting temperature is 400-800 ℃; purging the system in 5 stages by using one or more gases containing organic amine, oxygen, water vapor and ethanol at a certain flow rate as an activating gas; and when the gas outlet composition is consistent with the gas inlet after the 5 stages are finished, continuously purging for 0-24 h, and finishing regeneration.
The inert gas filled in the system is one or more of nitrogen, argon, helium and the like, and is preferably nitrogen.
The roasting temperature is higher than the highest temperature of gas liquid involved in the reaction, the temperature range is 400-800 ℃, and the temperature is preferably 450-600 ℃.
The activating gas used as the purge gas at least contains one or more of organic amine, oxygen, water vapor, ethanol, etc., and may optionally contain a portion of inert gas, such as nitrogen, argon, helium, etc., preferably no inert gas.
The organic amine is one or more of primary amine, secondary amine and tertiary amine, such as methylamine, ethylamine, ethylenediamine, etc.
Purging is divided into 5 stages: the volume concentration of oxygen in the 1 st stage is 5.0-12.5%, and the volume concentration of organic amine is 87.5-95%; the volume concentration of the oxygen in the 2 nd stage is 12.5-59.7%, and the volume concentration of the organic amine is 40.3-87.5%; the volume concentration of oxygen in the 3 rd stage is 59.7-79.2%, and the volume concentration of organic amine is 20.8-40.3%; in the 4 th stage, the water vapor volume concentration is 100 percent; in the 5 th stage, the volume concentration of the water vapor is 20.3-78.8%, and the volume concentration of the ethanol is 21.2-79.7%.
The 1 st stage to the 5 th stage, the volume airspeed of the mixed gas is 0.5 to 10 hours-1Preferably 1 to 3 hours-1。
When the gas outlet composition is consistent with the gas inlet after the 5 stages are finished, the purging time is continued for 0-24 h, preferably 1-2 h.
The catalyst regeneration gas purge pressure is preferably atmospheric pressure.
Detailed Description
The embodiments and the effects of the present invention are further illustrated by the following examples, but the scope of the present invention is not limited to the contents of the examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
In an experiment for preparing acetonitrile by ethanol in a laboratory, when the conversion per pass is reduced by 5 percent or the selectivity is reduced by 2 percent, the catalyst is judged to be deactivated and needs to be regenerated. And detecting the tail gas by using an oxygen analyzer, and judging that the gas outlet composition is consistent with the gas inlet composition when the oxygen content of the tail gas is consistent with the oxygen content of the gas inlet.
Example 1
The S-1 catalyst was prepared according to the procedure of example 1 of patent CN 102120589B.
160L of tetrapropylammonium hydroxide aqueous solution with the mass fraction of 5 percent is put into a reaction kettle, and a stirring paddle is started at the rotating speed of 50 revolutions per minute. Adding mixed solution of tetraethoxysilane and ethanol mixed according to the molar ratio of 20: 1 into the kettle at the speed of 5L/h, continuously stirring for 10min after the completion, and closing the kettle cover. Heating to 100 ℃ at the speed of 1 ℃/min, stopping reaction after 80 hours, cooling to room temperature, washing the obtained reaction liquid by a membrane filtration method until the pH of the filtrate is 10-11, removing impurities, drying the reaction liquid after removing the impurities, and roasting at 500 ℃ for 8 hours to obtain molecular sieve raw powder; the molar ratio of the tetrapropylammonium hydroxide to the tetraethoxysilane is 1: 132, a first step of removing the first layer; adding 60kg of silica sol with the mass fraction of 10%, 100g of polyethylene glycol 2000, 10kg of strong ammonia water, 1kg of sesbania powder and 1kg of activated carbon powder into 40kg of molecular sieve, kneading by a kneader, extruding into strips, molding, roasting at 500 ℃ for 8 hours, and taking out. Sequentially putting the roasted product into NH with the mass ratio of 2: 963-NH3NO3-H2Treating the mixed solution of O and hydrofluoric acid water solution with the mass fraction of 0.01% for 6h at 80 ℃, and washing the mixture by deionized water until the conductivity of the eluate is below 100 mu S/cm; taking out, drying, roasting at 500 deg.c for 8 hr, taking out and packing to obtain S-1 full-silicon molecular sieve. The particle size of the S-1 molecular sieve is 100-200 nm. The molecular sieve is in a strip shape, the diameter of the molecular sieve is 3mm, the length of the molecular sieve is 10mm, and the molecular sieve is used as a carrier A.
Example 2
The catalyst was prepared according to the procedure described in the example of patent CN 101602693B. 0.04g of potassium hydroxide, 1.09g of magnesium hydroxide, 1.41g of tin oxide, 7.35g of ammonium molybdate, 259.64g of catalyst A and 1038.58g of water are put into a rotary evaporator together, the temperature is raised to 60 ℃, and the water is drained under reduced pressure after the rotary evaporator rotates for 4 hours; drying the filter cake at 120 ℃, forming, roasting at 500 ℃ for 8h, and preparing the K of the all-silicon carrier0.2Mg6Sn3Mo12O48.1And the catalyst is numbered as catalyst B, and the catalyst is pressed into tablets, crushed and sieved to obtain 20-40 meshes of catalyst for evaluation experiment.
Example 3
50g of the catalyst B was loaded in a fixed bed, and the inner diameter of the reaction tube was 16 mm. The raw materials of ethanol and ammonia are vaporized and preheated to 200 ℃ respectively, the two raw materials are mixed and enter a raw material distributor from the upper part of a reactor and then enter a catalyst bed layer, and the reaction molar ratio of the two raw materials is that ethanol to ammonia is 1: 1. And cooling and collecting the reaction liquid, and controlling sampling. Ethanol conversion rate 96.3%, acetonitrile selectivity 78.7%. After 98h of operation, the ethanol conversion rate is 95.4%, and the acetonitrile selectivity is 76.6%. Deactivated catalyst number C.
Example 4
The catalyst C is regenerated and activated on line, firstly, the system is purged for 2h by using nitrogen at the temperature of 420 ℃, and the volume space velocity is 3h-1. The system was warmed to 600 ℃ and a nitrogen purge was maintained during this time. Temperature is reachedAt 600 ℃, activated gas is used for purging the system, and purging is divided into 4 stages: the volume concentration of oxygen in the 1 st stage is 10 percent, and the volume concentration of nitrogen is 90 percent; the volume concentration of oxygen in the 2 nd stage is 40 percent, and the volume concentration of nitrogen is 60 percent; the volume concentration of oxygen in the 3 rd stage is 60 percent, and the volume concentration of nitrogen is 40 percent; in the 4 th stage, the water vapor volume concentration is 100 percent; in stage 5, the water vapor volume concentration is 40.2%, and the ethanol volume concentration is 59.8%. Volume space velocity of activated gas 2h-1And when the inlet gas and the outlet gas have the same composition, continuing to purge for 1 h. The regenerated and activated catalyst was evaluated according to the procedure of example 3 for ethanol conversion of 96.1% and acetonitrile selectivity of 77.9%.
Example 5
The catalyst C is regenerated and activated on line, firstly, the system is purged for 2h by using nitrogen at the temperature of 420 ℃, and the volume space velocity is 3h-1. The system was warmed to 600 ℃ and a nitrogen purge was maintained during this time. When the temperature reaches 600 ℃, activated gas is used for purging the system, and purging is divided into 4 stages: the volume concentration of oxygen in the 1 st stage is 10 percent, and the volume concentration of methylamine is 90 percent; the volume concentration of oxygen in the 2 nd stage is 40 percent, and the volume concentration of methylamine is 60 percent; the volume concentration of oxygen in the 3 rd stage is 60 percent, and the volume concentration of methylamine is 40 percent; in the 4 th stage, the water vapor volume concentration is 100 percent; in stage 5, the water vapor volume concentration is 40.2%, and the ethanol volume concentration is 59.8%. Volume space velocity of activated gas 2h-1And when the inlet gas and the outlet gas have the same composition, continuing to purge for 1 h. The regenerated and activated catalyst was evaluated according to the procedure of example 3 for ethanol conversion of 96.2% and acetonitrile selectivity of 78.5%.
Example 6
The catalyst C is regenerated and activated on line, firstly, the system is purged for 2h by using nitrogen at the temperature of 420 ℃, and the volume space velocity is 3h-1. The system was warmed to 600 ℃ and a nitrogen purge was maintained during this time. When the temperature reaches 600 ℃, activated gas is used for purging the system, and purging is divided into 4 stages: the volume concentration of oxygen in the 1 st stage is 5 percent, and the volume concentration of methylamine is 95 percent; the volume concentration of oxygen in the 2 nd stage is 12.5 percent, and the volume concentration of methylamine is 87.5 percent; the volume concentration of oxygen in the 3 rd stage is 60.0 percent, and the volume concentration of methylamine is 40.0 percent; stage 4, the water vapor volume concentration is 100%(ii) a In stage 5, the water vapor volume concentration is 40.2%, and the ethanol volume concentration is 59.8%. Volume space velocity of activated gas 2h-1And when the inlet gas and the outlet gas have the same composition, continuing to purge for 1 h. The regenerated and activated catalyst was evaluated according to the procedure of example 3 for ethanol conversion of 96.1% and acetonitrile selectivity of 78.3%.
Example 7
The catalyst C is regenerated and activated on line, firstly, the system is purged for 2h by using nitrogen at the temperature of 420 ℃, and the volume space velocity is 3h-1. The system was warmed to 600 ℃ and a nitrogen purge was maintained during this time. When the temperature reaches 600 ℃, activated gas is used for purging the system, and purging is divided into 4 stages: the volume concentration of oxygen in the 1 st stage is 5 percent, the volume concentration of methylamine is 85 percent, and the volume concentration of nitrogen is 10 percent; the volume concentration of oxygen in the 2 nd stage is 12.5 percent, the volume concentration of methylamine is 77.5 percent, and the volume concentration of nitrogen is 10 percent; the volume concentration of oxygen in the 3 rd stage is 60.5%, the volume concentration of methylamine is 29.5%, and the volume concentration of nitrogen is 10%; in the 4 th stage, the water vapor volume concentration is 100 percent; in stage 5, the water vapor volume concentration is 40.2%, and the ethanol volume concentration is 59.8%. Volume space velocity of activated gas 2h-1And when the inlet gas and the outlet gas have the same composition, continuing to purge for 1 h. The regenerated and activated catalyst was evaluated according to the procedure of example 3 for ethanol conversion of 96.0% and acetonitrile selectivity of 78.1%.
Example 8
The catalyst C is regenerated and activated on line, firstly, the system is purged for 2h by using nitrogen at the temperature of 420 ℃, and the volume space velocity is 3h-1. The system was warmed to 600 ℃ and a nitrogen purge was maintained during this time. When the temperature reaches 600 ℃, activated gas is used for purging the system, and purging is divided into 4 stages: the volume concentration of oxygen in the 1 st stage is 5 percent, the volume concentration of methylamine is 85 percent, and the volume concentration of nitrogen is 10 percent; the volume concentration of oxygen in the 2 nd stage is 12.5 percent, the volume concentration of methylamine is 77.5 percent, and the volume concentration of nitrogen is 10 percent; the volume concentration of oxygen in the 3 rd stage is 60.5%, the volume concentration of methylamine is 29.5%, and the volume concentration of nitrogen is 10%; in the 4 th stage, the water vapor volume concentration is 100 percent; in stage 5, the water vapor volume concentration is 50.2%, and the ethanol volume concentration is 49.8%. Volume space velocity of activated gas 2h-1When the inlet gas and outlet gas have the same compositionAnd continuing purging for 1 h. The regenerated and activated catalyst was evaluated according to the procedure of example 3 for ethanol conversion of 96.1% and acetonitrile selectivity of 78.3%.
The above embodiments are all specific embodiments of the present invention, and the present invention is not limited by the above embodiments. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention, and it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
Claims (9)
1. A regeneration method of a catalyst for preparing acetonitrile from ethanol is characterized in that an inert gas is filled in a regeneration system of the catalyst; roasting the catalyst to be regenerated at a certain temperature, wherein the roasting temperature is 400-800 ℃; purging the system in 5 stages by using one or more gases containing organic amine, oxygen, water vapor and ethanol at a certain flow rate as an activating gas; and when the gas outlet composition of the activated gas is consistent with the gas inlet after each stage is finished, continuously purging for 0-24 h, and finishing regeneration.
2. The method of claim 1, wherein the activating gas comprises at least one or more of organic amine, oxygen, water vapor, ethanol, and the like.
3. The method of claim 2, wherein the activating gas further comprises an inert gas.
4. The method of claim 3, wherein the inert gas is selected from the group consisting of nitrogen, argon, helium.
5. The method according to claim 1, characterized in that the activation gas purge is divided into 5 phases: the volume concentration of oxygen in the 1 st stage is 5.0-12.5%, and the volume concentration of organic amine is 87.5-95%; the volume concentration of the oxygen in the 2 nd stage is 12.5-59.7%, and the volume concentration of the organic amine is 40.3-87.5%; the volume concentration of oxygen in the 3 rd stage is 59.7-79.2%, and the volume concentration of organic amine is 20.8-40.3%; in the 4 th stage, the water vapor volume concentration is 100 percent; in the 5 th stage, the volume concentration of the water vapor is 20.3-78.8%, and the volume concentration of the ethanol is 21.2-79.7%.
6. The method of claim 1 or 5, wherein the calcination temperature is higher than the highest temperature of the reaction-related gas feed liquid, and the temperature ranges from 400 ℃ to 800 ℃ from the 1 st stage to the 5 th stage.
7. The method according to claim 1 or 5, wherein the calcination temperature is higher than the highest temperature of the reaction-related gas feed liquid, and the temperature ranges from 400 ℃ to 600 ℃ from the 1 st stage to the 5 th stage.
8. The method according to claim 1 or 5, wherein the activation gas volume space velocity of the 1 st stage to the 5 th stage is 0.5 to 10 hours-1。
9. The method according to claim 1, wherein when the purging of the activation gas in each stage is finished and the composition of the outgassed gas and the composition of the fed gas are consistent, the continuous purging time is 1-2 h.
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